KR20140034882A - Preparation of new silicone diacrylate and its photosensitive resin composition - Google Patents

Abstract

The present invention provides a novel silicone diacrylate compound and a production method of the same. The present invention also provides a composite sheet with excellent thermal resistance and chemical resistance while having transparency by applying the silicone diacrylate compound. The silicone diacrylate compound is denoted by chemical formula 1. In the chemical formula 1, R1 is hydrogen or a methyl group; R2-R4 are a methyl group or a phenyl group; R5-R6 are hydrogen; and R7 is hydrogen or a phenyl group.

Description

Preparation method of new silicone diacrylate compound and photocuring composition using same {Preparation of new silicone diacrylate and its photosensitive resin composition}

The present invention relates to a novel silicon diacrylate-based compound, a method for producing the same, and a composite sheet for a display substrate including the same. More specifically, the present invention relates to a composite sheet having excellent transparency and excellent heat resistance and chemical resistance by synthesizing a silicon diacrylate-based compound having a specific structure and applying it as a binder including the same, and a display substrate using the same.

Glass which is excellent in heat resistance and chemical resistance and low in coefficient of linear expansion is widely used as a liquid crystal display element, an organic EL display element substrate, a color filter substrate, and a solar cell substrate. Recently, as a substrate material for display devices, miniaturization, thinning, weight reduction, impact resistance, and flexibility are required, plastic materials have been spotlighted as materials for replacing glass substrates.

Recently, materials such as polyethylene terephthalate (PET), polyether sulfone (PES), polyethylene naphthalate (PEN), polyarylate (PAR), polycarbonate (PC), and polyimide (PI) are used as plastic substrates. . However, these materials have a problem that the thermal expansion coefficient is considerably high, causing warpage or disconnection of the product. Polyimide-based resins have a relatively low coefficient of thermal expansion, but the problem is pointed out that they are not suitable as substrate materials due to their very low transparency and high birefringence and hygroscopicity.

In order to solve such a problem, Japanese Unexamined Patent Application Publication No. 2004-51960 discloses a transparent composite optical fiber produced from an alicyclic epoxy resin containing an ester group, a bisphenol A epoxy resin, an acid anhydride curing agent, and a catalyst and a glass fiber cloth Japanese Patent Application Laid-Open No. 2005-146258 discloses a transparent hybrid optical sheet made from an epoxy resin having an alicyclic epoxy resin and an dicyclopentadiene skeleton containing an ester group, an acid anhydride curing agent and a glass fiber cloth, -233851 discloses a transparent substrate made of a bisphenol A type epoxy resin, a bisphenol A novolac type epoxy resin, an acid anhydride type curing agent, and a glass fiber cloth. However, although the above patents satisfies the performance to some extent, there is a disadvantage in that the initial performance is degraded when exposed to a high temperature of 250 degrees or more or various solvents during the display panel manufacturing process.

An object of the present invention is to provide a novel silicone diacrylate-based compound and a method for producing the same.

Another object of the present invention is to provide a composite sheet having transparency and excellent heat resistance and chemical resistance by applying the silicone diacrylate-based compound.

The silicon diacrylate-based compound is represented by the following formula (1):

(Wherein R1 is hydrogen or methyl group, R2 to R4 is methyl or phenyl group, R5 and R6 are hydrogen, R7 is hydrogen or phenyl group)

The silicon diacrylate compound includes a step of preparing a silicon diol by reacting a trisiloxane compound represented by the following Formula 2 with allyl alcohol. This reaction was a known hydrosilylation reaction using Platinum (o) -divinyl-1,1,3,3-tetramethyldisiloxane (0.1 M in Xylene) as a catalyst. The solvent proceeds almost quantitatively in a 3 hour reaction at 70 ° C. using ethyl acetate. After the reaction, the solvent is removed using a rotary evaporator to obtain silicon diol with a yield of at least 85%. The silicon diol thus prepared may be reacted with 2 moles of acroyl chloride or methacroyl chloride in the presence of triethylamine as in Chemical Formula 3 to prepare a compound of Chemical Formula 1.

(Wherein R2 to R4 is a methyl group or a phenyl group, R5 and R6 are hydrogen, R7 is hydrogen or a phenyl group)

(Wherein R1 is hydrogen or methyl group, R2 to R4 is methyl or phenyl group, R5 and R6 are hydrogen, R7 is hydrogen or phenyl group)

Another aspect of the invention relates to a composite sheet. The composite sheet is characterized in that it comprises a silicone diacrylate compound represented by the formula (1) as a binder

The composite sheet includes a binder and a glass fiber sheet containing the silicon diacrylate compound. The glass fiber sheet may include one or more from the group consisting of glass fiber cloth, glass fabric, glass nonwoven fabric, glass mesh, glass beads, glass powder, and glass flake. have.

The present invention may include an impregnation process of preparing a glass fiber sheet in advance and impregnating the resin composition for forming a resin layer. The present invention can enable the resin composition for forming a resin layer to penetrate densely between the pores formed in the glass fiber sheet through such an impregnation process, and as a result, for forming the resin layer in the UV curing process proceeding to a later step When the resin composition is cured, it can be hardened so that no gap occurs at the interface with the glass fiber sheet, and when the final product is finished, it is possible to eliminate the cause of decrease in permeability and increase of haze by the void.

The amount of silicone diacrylate added is 1 to 20% by weight, most preferably 5 to 10% by weight. If the silicone diacrylate content is less than 1%, it is difficult to show sufficient viscosity to impregnate the glass fiber sheet, and it cannot exhibit sufficient heat resistance and chemical resistance, and when using more than 20% by weight, the dilution, heat resistance, and chemical resistance are excellent. However, there is a disadvantage in that the transparency of the sheet is lowered because the refractive index is not matched with the glass fiber sheet.

The refractive index of the silicone diacrylate in the present invention is in the range of 1.48 to 1.55.

The refractive index varies depending on the type of substituent. For example, a compound substituted with a methyl group (1 in Table 1) has the lowest refractive index as 1.48, and a compound substituted with a phenyl group (8 in Table 1) has a refractive index of 1.55. .

Therefore, it is important to select silicone diacrylate in consideration of dilution power and refractive index matching with glass fiber sheet.

In the present invention, in addition to the silicone diacrylate, it may include an acrylic monomer.

In the resin composition for forming a resin layer, the acrylic monomer is preferably a bifunctional or higher acrylic or methacryl compound, wherein the acrylic monomer is bisphenol-A diacrylate, bisphenol-S dimethacrylate, bisphenol-S di Acrylate, dicyclopentadienyl diacrylate, pentaerythritol triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, pentaerythritol tetraarc

Relate, bisphenol-A dimethacrylate, dicyclopentadienyl dimethacrylate, pentaerythritol trimethacrylate, tris (2-hydroxyethyl) isocyanurate trimethacrylate, and pentaerythritol Tetramethacrylate, a group consisting of ((2- (1- (acryloyloxy) -2-methylpropan-2-yl) -5-ethyl-1,3-dioxan-5-yl) methylacrylate It may be at least one selected from.

In the present invention, a high refractive index monomer may be included to match the refractive index of the glass fiber sheet and the resin forming layer. The monomer having high refractive index that can be used in the present invention

It is preferable that it is an acrylate containing a fluorene type compound which has two or more functional groups. Specific examples of the fluorene-based compound having a fluorene skeleton structure include 9,9-bis (4-hydroxyphenyl) fluorene , 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9 -Bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-

3-bromophenyl) fluorene, 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9 , 9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene and 9,9-bis (4-hydroxy It may be at least one acrylate containing a fluorene-based compound having a fluorene skeleton structure selected from the group consisting of oxy-3,5-dibromophenyl) fluorene.

The composition for forming a resin layer for forming the resin layer of the present invention further includes a photoinitiator in order to photocure them, in addition to the monomers described above. Here, the photoinitiator may select a conventional photoinitiator capable of photocuring the acrylic monomer.

The photoinitiators include Irgacure184, Irgacure 369, Irgacure 907, Irgacure OX01, Irgacure 242, Thioxanthone, 2,4-Diethyl Thioxanthone, Thioxanthone-4-sulfonic acid, Benzophenone, 4,4'-bis ( Diethylamino) benzophenone, acetophenone, p-dimethylami

Noacetophenone, α, α'-dimethoxyacetoxy benzophenone, 2,2'-dimethoxy-2-petylacetophenone, p-methoxyacetophenone, 2-methyl [4- (methylthio) phenyl]- 2-morpholino-1-propaneone, 2-benzyl-2-diethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-hydroxy-2-methyl-1-phenyl Ketones such as propan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, and 1-hydroxycyclohexyl phenylketone; Quinones such as anthraquinone and 1,4-naphthoquinone;

1,3,5-tris (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2-chlorophenyl) -s-triazine, 1,3-bis (trichloro Rophenyl) -s-triazine, phenacylchloride, tribromomethylphenylsulfone,

Halogen compounds such as tris (trichloromethyl) -s-triazine; Peroxides such as di-t-butyl peroxide; Acyl phosphine oxides such as 2,4,6-trimethyl benzoyl diphenyl phosphine oxide; can be used. In the present invention, the photoinitiators may be used alone or in combination.

The content of the photoinitiator may have a range of 0.5 to 5% by weight based on 100% by weight of the total resin layer forming composition. If the content of the photopolymerization initiator is less than 0.5% by weight, the sensitivity is not sufficient, and the acrylic polymerization conversion rate is 90% or less, so that uncured monomers remain hard to have basic optical properties of the substrate. In addition, when the content of the photoinitiator exceeds 10% by weight, light transmittance, haze, yellow index, etc. of the substrate tend to be lowered.

In addition, it may further include additives such as surfactants, curing accelerators, antioxidants for the expression of special functions.

The present invention provides a novel silicone diacrylate compound and a method of manufacturing the same, the silicone diacrylate compound has a low viscosity and excellent processability in the glass fiber impregnation process, the composite sheet prepared by including the heat-resistant and heat-resistant It is characterized by excellent chemical properties. The composite sheet has the effect of providing a display substrate that can be miniaturized, thin, lightweight, and low cost.

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

Details that are not described herein will be omitted since those skilled in the art can sufficiently infer technically.

Production Example 1

Synthesis of Silicon Diol

300 ml of ethyl acetate was added to a 1000 ml flask equipped with a condenser and a thermometer and stirred. 166g (0.5mol) of hexamethyltrisiloxane and 134g (1mol) of allyl alcohol are added and then 0.05g of Platinum (o) -divinyl-1,1,3,3-tetramethyldisiloxane (0.1 M in Xylene) is added as a catalyst. The reaction progress was monitored using gas chromatography at intervals of 1 hour while the reaction was in progress. After 5 hours the temperature was lowered and the solvent was removed using a rotary evaporator to obtain the desired silicon diol.

<Synthesis of Silicon Diacrylate>

300 ml of ethyl acetate was added to a 1000 ml flask equipped with a condenser and a thermometer. Then, 178 g (0.4 mol) of silicon diol, 90 g (1 mol) of acryloyl chloride, and Butylated Hydroxy Toluene (BHT) obtained in the above reaction were added at 70 degrees. Stir for 5 hours.

After the reaction was completed, the reactant was put in a 3L separatory funnel, 800 ml of ethyl acetate was added, and washed three times with 1000 ml of 20% -KOH solution. After the solvent was removed from the rotary evaporator, the residual solvent was further removed by a vacuum pump to synthesize a desired silicon diarylate.

Production Example 2

Except for using acryloyl chloride instead of acryloyl chloride in Preparation Example 1 was carried out in the same manner as in Preparation Example 1.

Production Example 3

The preparation was carried out in the same manner as in Preparation Example 1, except that 1-Allyl phenol was used instead of allyl alcohol in Preparation Example 1.

Production Example 4

Except for using 1-Allyl phenol instead of allyl alcohol in methacryloyl chloride instead of acryloyl chloride in Preparation Example 1 was carried out in the same manner as in Preparation Example 1.

Production Example 5

The preparation was carried out in the same manner as in Preparation Example 1, except that Diphenyl tetramethyl trisiloxane was used instead of Hexamethyl trisiloxane.

Production Example 6

Diphenyl tetramethyl trisiloxane in place of Hexamethyl trisiloxane in Preparation Example 1 was carried out in the same manner as in Preparation Example 1 except that methacroyl chloride was used instead of acryloyl chloride.

Production Example 7

Diphenyl tetramethyl trisiloxane instead of Hexamethyl trisiloxane in Preparation Example 1 was carried out in the same manner as in Preparation Example 1 except that 1-Allyl phenol was used instead of allyl alcohol.

Production Example 8

Diphenyl tetramethyl trisiloxane instead of hexamethyl trisiloxane in Preparation Example 1 was carried out in the same manner as in Preparation Example 1 except that 1-Allyl phenol instead of allyl alcohol and methacroyl chloride instead of acryloyl chloride.

Production Example 9

Except for using Hexaphenyl trisiloxane instead of Hexamethyl trisiloxane in Preparation Example 1 was carried out in the same manner as in Preparation Example 1.

Preparation Example 10

Except that Hexaphenyl trisiloxane instead of Hexamethyl trisiloxane in Preparation Example 1 was used in the same manner as in Preparation Example 1 except that methacroyl chloride instead of acryloyl chloride.

Preparation Example 11

The preparation was carried out in the same manner as in Preparation Example 1, except that 1-Allyl phenol was used instead of allyl alcohol instead of Hexaphenyl trisiloxane instead of Hexamethyl trisiloxane.

Preparation Example 12

Except that Hexaphenyl trisiloxane instead of Hexamethyl trisiloxane in Preparation Example 1 was carried out in the same manner as in Preparation Example 1 except that 1-Allyl phenol instead of allyl alcohol and methacroyl chloride instead of acryloyl chloride.

Example 1 Preparation of Composite Sheet

1.0 g of silicone diacrylate (A, Preparation Example 1) synthesized in Preparation Example 1, 5.0 g of bisphenol-A diacrylate (B), 3.0 g of pentaerythritol trimethacrylate (C), 9,9- 1.0 g of bis (4-hydroxyphenyl) fluorene (D) and 0.2 g of Irgacure184 (E) Mix well. After impregnating the composition with 10 g of E-glass-based glass fiber (manufactured by Nittobo, product name 3313), the glass substrate was placed between release-treated glass substrates and irradiated with UV for 2 minutes on both sides. The composite time was obtained.

The heat resistance and chemical resistance of the composite sheet thus obtained were evaluated, respectively. The evaluation results are shown in Table 2.

Examples 2-5

Except for changing the amount of silicone diacrylate in Example 1 was carried out in the same manner as in Example 1.

Comparative Example 1

The composite sheet was prepared and evaluated in the same manner as in Example 1, except that the amount of bisphenol-A diacrylate used was 6.0 g without using silicone diacrylate in Example 1.

 Performance Evaluation of Composite Sheet (Unit: g)                         Composition water       Evaluation results     A     B     C     D     E Heat resistance Chemical resistance Example 1    1.0    5.0    3.0    1.0    0.2   Great    ○ Example 2    0.5    5.5    3.0    1.0    0.2   Great    ○ Example 3    0.1    5.9    3.0    1.0    0.2   Inadequate    ○ Example 4    2.0    3.0    3.0    1.0    0.2   Great    ○ Example 5    3.0    2.5    3.0    1.0    0.2   Great    ○ Comparative Example 1     -    6.0    3.0    1.0    0.2   Bad    ×

Heat resistance evaluation

The composite sheet obtained by the above method was measured for chromaticity (b) using a spectrophotometer (MCPD3000, manufactured by Otsuka Electronics), and then treated for 2 hours in an oven at 250 ° C., and then measured for chromaticity (b).

<Evaluation Criteria>

Excellent: b value change less than 0.1 after 2 hours treatment at 250 ℃ oven

Inadequate: b value change from 0.1 to 1.0 after treatment for 2 hours in an oven at 250 ℃

Poor: b value change over 1.0 after 2 hours in 250 ℃ oven

Chemical resistance evaluation

After heating the vial containing N-methyl-2-pyrrolidone (NMP) and EP6 (including Tetramethylammonium hydroxide, manufactured by Homming Industries Co., Ltd.) to 60 ° C., The composite sheet obtained by the method was continuously dipped for 10 minutes, taken out, and washed with deionized water (DIW). The washed specimen was dried at 200 ° C. for about 20 minutes in a hot air circulation drying furnace. After repeating this process three times in total, the chromaticity b was measured using a spectrophotometer (MCPD3000, Otsuka Electronics).

<Evaluation Criteria>

 (Circle): Color (b) change before and after chemical resistance evaluation is 0.1 or less

 (Triangle | delta): The color (b) change before and after chemical resistance evaluation is 0.1-1.0

X: Color (b) change before and after chemical resistance evaluation is 1.0 or more

Claims (2)

UV curable composition containing a compound (A) represented by the following formula (1), a reactive monomer (B), and a photoinitiator

[Chemical Formula 1]

In Formula 1, R1 is hydrogen or methyl group, R2 in R2 is methyl group or phenyl group, R5 and R6 are hydrogen, R7 is hydrogen or phenyl group.
Flexible display substrate prepared by impregnating the compound represented by Formula 1 of claim 1 in a glass fiber layer